US9637619B2 - Polysulfide mixtures, method for the production thereof, and use of the polysulfide mixtures in rubber mixtures - Google Patents

Polysulfide mixtures, method for the production thereof, and use of the polysulfide mixtures in rubber mixtures Download PDF

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US9637619B2
US9637619B2 US14/434,892 US201314434892A US9637619B2 US 9637619 B2 US9637619 B2 US 9637619B2 US 201314434892 A US201314434892 A US 201314434892A US 9637619 B2 US9637619 B2 US 9637619B2
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compounds
formula
mixture
rubber
polysulfide
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US20150284547A1 (en
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Ulrich Feldhues
Heinz Unterberg
Hermann-Josef Weidenhaupt
Melanie Wiedemeier-Jarad
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Lanxess Deutschland GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/14—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/247—Heating methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2481/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to novel polysulfide mixtures, to processes for the production of said polysulfide mixtures, to the use of the polysulfide mixtures in rubber mixtures, to rubber vulcanizates produced therefrom, and to use of these.
  • Silica-containing rubber mixtures are important starting materials, for example for the production of tires with reduced rolling resistance. These consume less rolling deformation energy, and therefore reduce fuel consumption. Because various states have decided on compulsory marking to indicate rolling resistance on tires, there is a high level of interest in achieving a further reduction in this resistance.
  • the rubber mixture initially prepared with the additives In the processing of rubbers it is advantageous for the rubber mixture initially prepared with the additives to have low viscosity (Mooney viscosity ML 1+4/100° C.), and thus to have good processability.
  • Other additional substances have been proposed for improving the processability of silica-containing rubber mixtures, examples being fatty acid esters, fatty acid salts, and mineral oils.
  • the additional substances mentioned have the disadvantage of that, although they increase flowability, they greatly reduce moduli at relatively high elongation (e.g. from 100% to 300%) or the hardness of the vulcanizates, thus impairing the reinforcing effect of the filler. Inadequate hardness or stiffness of the vulcanizate leads to unsatisfactory running performance of the tire, particularly around curves.
  • the hardness of the vulcanizate can be increased by increasing the proportion of reinforcing filler, or by reducing the proportion of plasticizer oil, but each of these two measures has the disadvantage of causing higher mixture vis
  • EP 0 489 313 describes additives comprising glycol functions and having good mechanical properties and improved hysteresis performance.
  • the examples reveal no improvement in roiling resistance (tan ⁇ at 60° C.).
  • the polysulfide mixture disclosed comprises polysulfides of the formulae (II), (III), (IV), (V), and (VI):
  • the polysulfide mixture disclosed by Arisawa et al. comprises about
  • the high proportion of compound (II) also inhibits use in rubber mixtures.
  • This has relatively low molecular weight (238.3), relatively taw flashpoint (150° C.), and a strong unpleasant odor. It moreover comprises only sulfur atoms bonded to at least one carbon atom, and comprises no sulfur atoms bonded only to sulfur atoms, the latter being more easily available for reactions and being termed hereinafter active sulfur atoms.
  • the mixture disclosed by Arisawa et al. therefore comprises on average less than three sulfur atoms per molecule, and therefore comprises on average less than one active central sulfur atom per molecule.
  • the use of this polysulfide mixture achieved an improvement in Mooney viscosity and hardness, but at the cost of markedly increased rolling resistance and abrasion, and the polysulfide is therefore not ideal for the use in tires.
  • each of the two moieties R is identical or different, preferably identical, and is methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, or C 5 -alkyl, C 6 -alkyl, C 7 -alkyl, or C 8 -alkyl, preferably methyl, ethyl, n-propyl, n-butyl, or isooctyl, particularly preferably methyl, and n is a number from 2 to 6.
  • polysulfide mixtures which comprise asymmetric polysulfides, i.e. polysulfides which bear two different substituents R.
  • VI alkyl mercaptopropionates
  • mixtures of this type are to be considered as equivalent to the mixtures of polysulfides having identical substituents R.
  • the preferred embodiment of the present invention involves a polysulfide mixture of symmetrical polysulfides, i.e. involves polysulfides which bear two identical substituents, in particular mixtures in which R is identical in all of the polysulfides.
  • the contact between the materials typically takes place in an inert medium, and this means a medium which, under the reaction conditions, undergoes reaction with the reactants to an extent of at most 10%, preferably at most 5%, particularly preferably at most 1%, and very particularly preferably 0%.
  • a suitable medium is preferably any of the following that are liquid under reaction conditions: aliphatic cyclic and/or acyclic hydrocarbons, aromatic hydrocarbons, aliphatic and/or aromatic halohydrocarbons, ethers, and esters, and mixtures thereof.
  • Particularly preferred media are toluene and cyclohexane, it is preferable to use anhydrous media.
  • the materials are brought into contact in a mixture of polysulfides of the formula (I), in particular of the polysulfide mixtures of the invention described above, and it is thus possible to omit the removal of the inert medium.
  • the contact between materials typically takes place at temperatures of from 0° C. to 60° C., preferably from 10° C. to 45° C., particularly preferably from 15° C. to 35° C. If temperatures are too low, S 2 Cl 2 is not necessarily immediately consumed in the reaction, and this can lead to potential risks and to byproducts resulting from build-up of a relatively high concentration of S 2 Cl 2 in the reaction mixture. Excessively high temperatures should likewise be avoided for reasons of occupational safety and of product quality.
  • all or some of the resultant HCl gas is removed from the mixture before the end of the reaction, in particular via passage of inert gas through the reaction mixture and/or via application of vacuum, i.e. of a pressure of less than 1013 mbar.
  • a polysulfide mixture of the invention is used as inert medium, removal of the inert medium is omitted.
  • the removal of said inert medium takes place at a temperature no higher than 45° C., preferably no higher than 40° C., particularly preferably no higher than 35° C., and very particularly preferably no higher than 30° C., and is preferably carried out at reduced pressure, i.e. less than 1013 mbar.
  • both the contact between alkyl 3-mercaptopropionates (VII) and S 2 Cl 2 and the removal of an inert medium, insofar as this is not a polysulfide mixture of the invention, are effected in the temperature range from 10° C. to 45° C., particularly from 15° C. to 35° C., very particularly from 20° C. to 30° C.
  • the present invention provides not only the process for the production of polysulfide mixtures of the invention but also the resultant polysulfide mixtures of the formula (I), where the two moieties R are identical or different, preferably identical, and are methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, or C 5 -alkyl, C 6 -alkyl, C 7 -alkyl, or C8-alkyl preferably methyl, ethyl, n-propyl, n-butyl, or isooctyl, particularly preferably methyl, and n is a number from 2 to 6.
  • the quantitative data relating to the compounds of the formula (I) are area percentage data from the type of HPLC measurement described near the end of example 3, using refractive index (RI) defector.
  • the polysulfide mixture of the invention comprises less than 10%, particularly less than 3%, very particularly less than 1%, and most preferably less than 0.2%, of byproducts or admixtures, i.e. compounds which do not correspond to the formula (I).
  • the polysulfide mixture of the invention typically comprises less than 2%, preferably less than 1%, particularly preferably lass than 0.3%, very particularly preferably less than 0.1%, and most preferably 0%, of elemental sulfur as admixture.
  • the flashpoint of a polysulfide mixture of the invention is usually above 180° C., preferably above 200° C.
  • the sulfur content of the polysulfide mixture of the invention is usually, from elemental analysis, from 35 to 50%, preferably from 40 to 45%.
  • the typical total chlorine content of a polysulfide mixture of the invention is ⁇ 1000 ppm, preferably ⁇ 100 ppm, particularly preferably ⁇ 10 ppm.
  • the number of sulfur atoms in the polysulfide mixture of the invention is usually on average, per molecule of the formula (I), from 3.5 to 4.5, preferably from 3.7 to 4.3, particularly preferably from 3.8 to 4.2, very particularly preferably from 3.9 to 4.1.
  • the number of active sulfur atoms in the polysulfide mixture of the invention is therefore typically on average, per molecule of the formula (I), from 1.5 to 2.5, preferably from 1.7 to 2.3, particularly preferably from 1.8 to 2.2, very particularly preferably from 1.9 to 2.1.
  • the polysulfide mixtures of the formula (I) of the invention are preferably stored at temperatures of from 0 to 35° C., in particular from 0 to 20° C.
  • the polysulfide mixtures of the invention exhibit unexpected properties when used in rubber mixtures, in comparison with a reference mixture without the polysulfide mixture of the invention, there was an improvement in flowability and scorch time of the mixture, and in the hardness and the rolling resistance of the vulcanizate. This is all the more astonishing because the mixture used in EP 11164319 comprising 65% of the compound (IV) and 31% of the compounds (III) and (V), i.e. comprising comparable content of active sulfur atoms, causes marked impairment of rolling resistance and abrasion in comparison with the reference mixture.
  • the invention therefore also provides rubber mixtures comprising respectively at least one rubber and one polysulfide mixture of the invention.
  • the invention provides rubber mixtures comprising respectively at least one rubber, one sulfur-containing alkoxysilane, one silica-based filler, and one polysulfide mixture of the invention.
  • the polysulfide mixtures of the invention can also to some extent or entirely be used after absorption on inert, organic, or inorganic carriers.
  • Preferred carrier materials are silica, natural and synthetic silicates, aluminum oxide, and/or carbon blacks.
  • the total content of polysulfide mixture of the invention in the rubber mixtures in the invention is preferably from 0.1 to 15 phr, particularly from 0.3 to 7 phr, very particularly from 0.5 to 3 phr, and most preferably from 0.7 to 1.5 phr.
  • the unit phr represents parts by weight based on 100 parts by weight of rubber used in the rubber mixture.
  • Natural rubber and/or synthetic rubbers can be used for the production of the rubber mixtures of the invention.
  • Examples of preferred synthetic rubbers are:
  • NBR butadiene/acrylonitrile copolymers with from 5 to 60% by weight, preferably from 10 to 50% by weight, acrylonitrile content
  • HNBR partially or fully hydrogenated NBR rubber
  • the rubber mixtures of the invention comprise at least one SBR rubber and at least one BR rubber, particularly in an SBR:BR ratio by weight of from 60:40 to 90:10.
  • the rubber mixtures of the invention moreover comprise at least one NR rubber. It is particularly preferable that they comprise at least one SBR rubber, at least one BR rubber, and at least one NR rubber, where the ratio by weight of SBR rubber to BR rubber to NR rubber is very particularly preferably from 60 to 85; from 10 to 35: from 5 to 20.
  • sulfur-containing alkoxysilanes suitable for the rubber mixtures of the invention are bis(triethoxysilylpropyl) tetrasulfane (e.g. Si 69 from Evonik) and bis(triethoxysilylpropyl) disulfane (e.g. Si 75 from Evonik), 3-(triethoxysilyl)-1-propanethiol, polyether-functionalized mercaptosilanes such as Si 363 from Evonik, and thioester-functionalized alkoxysilanes such as NXT or NXT Z from Momentive (previously GE). It is also possible to use mixtures of the sulfur-containing alkoxysilanes.
  • Liquid sulfur-containing alkoxysilanes may be applied to a support in order to increase ease of metering and/or dispersibility (dry liquid).
  • the active ingredient content is between 30 and 70 parts by weight, preferably 40 and 60 parts by weight, per 100 parts by weight of dry liquid.
  • the proportion of the sulfur-containing alkoxysilanes in the inventive rubber mixtures is preferably 2 to 20 phr, more preferably 3 to 11 phr and most preferably 5 to 8 phr, calculated in each case as 100% active ingredient. It is preferable that the quantity of sulfur-containing alkoxysilane is greater than or equal to the quantity of the polysulfide mixture of the formula (I) of the invention.
  • the ratio by weight of sulfur-containing alkoxysilane to the polysulfide mixture of the formula (I) of the invention is particularly preferably from 1.5:1 to 20:1, very particularly preferably from 3:1 to 15:, and most preferably from 5:1 to 10:1.
  • the rubber mixture preferred in the invention moreover comprises one or more silica-based fillers.
  • Substances preferably used here are the following:
  • Carbon blacks produced by the lamp-black, furnace-black, or gas-black process are particularly suitable for this purpose where the BET surface areas of these are from 20 to 200 m 2 /g, examples being SAF, ISAF, IISAF, HAF, FEF, and GPF carbon blacks.
  • the total content of fillers is preferably from 10 to 200 phr, particularly preferably from 50 to 160 phr, and very particularly preferably from 60 to 120 phr.
  • a particularly preferred embodiment is provided by the combination of silica, carbon black, and polysulfide mixture of the invention.
  • the ratio of silica to carbon black here can vary within any desired limits, but for the application in tires preference is given to a silica:carbon black ratio by weight of from 20:1 to 1.5:1.
  • the rubber mixtures of the invention also comprise one or more crosslinking agents.
  • Sulfur-based or peroxidic crosslinking agents are particularly suitable for this purpose, and particular preference is given here to sulfur-based crosslinking agents.
  • Peroxidic crosslinking agents preferably used are bis(2,4-dichlorobenzyl) peroxide, dibenzoyl peroxide, bis(4-chlorobenzoyl) peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl perbenzoate, 2,2-bis(tert-butylperoxy)butanes 4,4-di-tert-butylperoxynonyl valerate, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl cumyl peroxide, 1,3-bis(tert-butylperoxyisopropyl)benzene, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne.
  • Sulfur can be used as crosslinking agent in elemental soluble or insoluble form, or in the form of sulfur donors.
  • sulfur donors that can be used are dimorpholyl disulfide (DTDM), 2-morpholinodithiobenzothiazole (MBSS), caprolactam disulfide, dipentamethylenethiuram tetrasulfide (DPTT), and tetramethylthiuram disulfide (TMTD).
  • DTDM dimorpholyl disulfide
  • MBSS 2-morpholinodithiobenzothiazole
  • DPTT dipentamethylenethiuram tetrasulfide
  • TMTD tetramethylthiuram disulfide
  • the crosslinking of the rubber mixtures of the invention can in principle be achieved with sulfur or sulfur donors alone, or in conjunction with vulcanization accelerators, examples of compounds suitable for these being dithiocarbamates, thiurams, thiazoles, sulfenamides, xanthogenates, bi- or polycyclic amines, guanidine derivatives, dithiophosphates, caprolactams, and thiourea derivatives.
  • Other compounds suitable are moreover zinc diamine diisocyanate, hexamethylenetetramine, 1,3-bis(citraconimidomethyl)benzene, and also cyclic disulfanes.
  • the rubber mixtures of the invention comprise sulfur-based crosslinking agents and vulcanization accelerators.
  • Crosslinking agents particularly preferably used are sulfur, magnesium oxide, and/or zinc oxide; the known vulcanization accelerators such as mercaptobenzothiazoles, thiazolsulfenamides, thiurams, thiocarbamates, guanidines, xanthogenates, and thiophosphates are added to these.
  • Preferred quantities used of the crosslinking agents and vulcanization accelerators are from 0.1 to 10 phr, particularly from 0.1 to 5 phr.
  • the rubber mixtures of the invention can comprise other rubber auxiliaries, such as reaction accelerators, aging inhibitors, heat stabilizers, light stabilizers, antioxidants, and in particular antiozonants, flame retardants, processing aids, impact-resistance improvers, plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarders, metal oxides, and activators, in particular triethanolamine, polyethylene glycol, hexanetriol, and anti-reversion agents.
  • reaction accelerators reaction accelerators, aging inhibitors, heat stabilizers, light stabilizers, antioxidants, and in particular antiozonants, flame retardants, processing aids, impact-resistance improvers, plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarders, metal oxides, and activators, in particular triethanolamine, polyethylene glycol, hexanetriol, and anti-reversion agents.
  • Preferred aging inhibitors used are alkylated phenols, styrenated phenol, sterically hindered phenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol (BHT), 2,6-di-tert-butyl-4-ethylphenol, sterically hindered phenols containing ester groups, sterically hindered phenols containing thioether, 2,2′-methylenebis-(4-methyl-6-tert-butylphenol) (BPH), and also sterically hindered thiobisphenols.
  • alkylated phenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol (BHT), 2,6-di-tert-butyl-4-ethylphenol, sterically hindered phenols containing ester groups, sterically hindered phenols
  • aminic aging inhibitors e.g. mixtures of diaryl-p-phenylenediamines (DTPD), octylated diphenylamine (ODPA), phenyl- ⁇ -naphthylamine (PAN), phenyl- ⁇ -naphthylamine (PBN), preferably those based on phenylenediamine, e.g.
  • N-isopropyl-N′-phenyl-p-phenylanediamine N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine (6PPD), N-1,4-dimethylpentyl-N′-phenyl-p-phenylenediamine (7PPD), N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine (77PD).
  • aging inhibitors are phosphites such as tris(nonylphenyl) phosphite, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), 2-mercaptobenzimidazole (MBI), methyl-2-mercaptobenzimidazole (MMBI), zinc methylmercaptobenzimidazole (ZMMBI), these mostly being used in combination with above phenolic aging inhibitors.
  • TMQ, MBI, and MMBI are mainly used for NBRs, where these are vulcanized peroxidically.
  • Ozone resistance can be improved via antioxidants such as N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine (6PPD), N-1,4-dimethylpentyl-N′-phenyl-p-phenylenediamine (7PPD), N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine (77PD), enol ethers, or cyclic acetals.
  • antioxidants such as N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine (6PPD), N-1,4-dimethylpentyl-N′-phenyl-p-phenylenediamine (7PPD), N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine (77PD), enol ethers, or cyclic acetals.
  • Processing aids are intended to act between the rubber particles, and to counteract frictional forces during mixing, plastification, and deformation.
  • Processing auxiliaries which may be present in the rubber mixtures of the invention comprise all the lubricants conventionally used for the processing of plastics, for example hydrocarbons such as oils, paraffins and PE waxes, fatty alcohols having from 6 to 20 carbon atoms, ketones, carboxylic acids such as fatty acids and montan acids, oxidized PE wax, metal salts of carboxylic acids, carboxamides, and carboxylic esters, for example with the alcohols ethanol, fatty alcohols, glycerol, ethanediol, pentaerythritol, and long-chain carboxylic acids as acid component.
  • the rubber mixture composition of the invention can also comprise flame retardants in order to reduce flammability, and to reduce smoke generation during combustion.
  • flame retardants examples include antimony trioxide, phosphoric esters, chloroparaffin, aluminum hydroxide, boron compounds, zinc compounds, molybdenum trioxide, ferrocene, calcium carbonate, and magnesium carbonate.
  • plastics are preferably selected from the group consisting of homo- and copolymers based on ethylene, propylene, butadiene, styrene, vinyl acetate, vinyl chloride, glycidyl acrylate, glycidyl methacrylate, or on acrylates or methacrylates having alcohol components of branched or unbranched C 1 to C 10 alcohols, particular preference being given to polyacrylates having identical or different alcohol moieties from the group of the C 4 to C 8 alcohols, in particular of butanel, hexanol, octanol and 2-ethylhexanol, and to polymethyl methacrylate, methyl methacrylate-butyl acrylate copolymers, methyl methacrylate-butyl methacrylate copolymers, ethylene-vin
  • the rubber mixture of the invention comprises from 0.1 to 15 phr of the anti-reversion agent 1,6-bis(N,N-dibenzylthiocarbamoyldithio)hexane (CAS No.; 151900-44-6), permitting a further reduction in rolling resistance.
  • a preferred feature of the rubber mixtures of the Invention is that the loss factor tan ⁇ at 60° C. of a vulcanizate produced therefrom under 170° C./t95 heating conditions is ⁇ 0.12, while its Shore A hardness at 23° C. is >68.
  • the inventive rubber mixtures can also achieve a vulcanization time of less than 2000 seconds, and particularly preferably a scorch time of from 500 to 1000 seconds.
  • the present invention further provides a process for the production of rubber mixtures via mixing of at least one rubber with a polysulfide mixture of the invention. It is moreover preferable to admix at least one silica-based filler, and at least one sulfur-containing alkoxysilane.
  • filler particularly from 30 to 120 phr, and very particularly from 50 to 100 phr, from 0.1 to 15 phr of polysulfide mixture of the invention, particularly from 0.3 to 7 phr, very particularly from 0.5 to 3 phr, and most preferably from 0.7 to 1.5 phr, and from 2 to 20 phr of the sulfur-containing alkoxysilane, particularly from 3 to 11 phr, and very particularly from 5 to 8 phr.
  • additional fillers, crosslinking agents, vulcanization accelerators, and rubber auxiliaries preferably in the quantities stated above.
  • the addition of the polysulfide mixture of the invention preferably takes place in the first part of the mixing process, the addition of one or more crosslinking agents, in particular sulfur, and optionally vulcanization accelerators, taking place in a subsequent mixing stage.
  • the temperature of the rubber composition here is preferably from 100 to 20° C., particularly preferably from 120° C. to 170° C.
  • the shear rates for the mixture during mixing are from 1 to 1000 sec ⁇ 1 , preferably from 1 to 100 sec ⁇ 1.
  • the rubber mixture is cooled after the first mixing stage, and the crosslinking agent and optionally crosslinking accelerator, and/or additions used to increase crosslinking yield are added in a subsequent mixing stage at ⁇ 140° C., preferably ⁇ 100° C. It is equally possible to add the polysulfide mixture of the invention in a subsequent mixing stage and at relatively low temperatures, for example from 40 to 100° C., for example together with sulfur and crosslinking accelerator.
  • Conventional mixing assemblies such as rolls, internal mixers, and mixing extruders, can be used to blend the rubber with the filler and with the polysulfide mixture of the invention.
  • 1,6-bis(N,N-dibenzylthiocarbamoyldithio)hexane preferably takes place in the first stage of the multistage mixing process.
  • the present invention further provides a process for the vulcanization of the rubber mixtures of the invention which is preferably carried out with temperatures of the composition of from 100 to 200° C., particularly from 130 to 180° C. In one preferred embodiment, the vulcanization takes place at a pressure of from 10 to 200 bar.
  • the present invention also comprises rubber vulcanizates obtainable via vulcanization of the rubber mixtures of the invention.
  • the present invention further comprises rubber products comprising said vulcanizates.
  • tires since corresponding tires have the advantage of high hardness coupled with good rolling resistance.
  • the present invention therefore also comprises vehicles comprising rubber products which include the vulcanizates of the invention.
  • the rubber vulcanizates of the invention are suitable for the production of moldings with improved properties, e.g. for the production of cable sheathing, of fuses, of drive belts, of conveyor belts, of roll coverings, of tires, of shoe soles, of sealing rings, and of damping elements.
  • the rubber vulcanizate of the invention can moreover be used for the production of foams.
  • chemical or physical blowing agents are added thereto. Any of the substances known for this purpose can be used as chemical blowing agents, for example azodicarbonamide, p toluenesulfonyl hydrazide, 4,4′-oxybis(benzenesulfohydrazide), p-toluenesulfonyl semicarbazide, 5-phenyltetrazole, N,N′-dinitrosopentamethylenetetramine, zinc carbonate, or sodium hydrogencarbonate, and mixtures comprising these substances.
  • suitable physical blowing agents are carbon dioxide and halogenated hydrocarbons.
  • the present invention further provides the use of the polysulfide mixture of the invention for the production of rubber mixtures, and of vulcanizates thereof, and in particular for the production of rubber mixtures comprising at least respectively one rubber, one sulfur-containing alkoxysilane, and one silica-based filler.
  • the present invention further provides the use of the polysulfide mixture of the invention for the production of additive compositions for rubbers.
  • additive compositions for rubbers comprising at least one sulfur-containing alkoxysilane, in particular bis(triethoxysilylpropyl) tetrasulfane, bis(triethoxysilylpropyl) disulfane, 3-(triethoxysilyl)-1-propanethiol, polyether-functionalized mercaptosilane, or thioester-functionalized alkoxysilane, and the polysulfide mixture of the invention have sufficient compatibility of the components, despite the reactive groups, thus permitting homogeneous incorporation into rubber mixtures and precise metering in the desired ratio.
  • sulfur-containing alkoxysilane in particular bis(triethoxysilylpropyl) tetrasulfane, bis(triethoxysilylpropyl) disulfane, 3-(triethoxysilyl)-1-propanethiol, polyether-functionalized mercaptosilane, or thioester-functionalized alk
  • the present invention therefore also comprises additive compositions of this type for rubbers, and also the use of the polysulfide mixtures of the invention for the production of additive compositions of this type.
  • the ratio by weight of alkoxysilane, in particular of bis(triethoxysilylpropyl) tetrasulfane and/or of bis(triethoxysilylpropyl) disulfane, to the polysulfide mixtures of the invention in these additive compositions is preferably from 1.5:1 to 20:1, particularly preferably from 3:1 to 15:1, and very particularly preferably from 5:1 to 10:1.
  • the present invention moreover comprises a process for the production of additive compositions for rubbers, characterized in that sulfur-containing alkoxysilanes are mixed with the polysulfide mixtures of the invention.
  • the present invention further comprises a process for reducing the rolling resistance of fires, where a polysulfide mixture of the invention is mixed with a non-crosslinked or partially crosslinked rubber mixture serving as starting material for at least parts of the fire, and the mixture is then vulcanized.
  • the viscosity can be determined directly from the force with which the rubbers (and rubber mixtures) resist processing thereof.
  • Mooney shearing disk viscometer a fluted disk is enclosed, above and below, by test substance and is rotated at about two revolutions per minute in a beatable chamber. The force required here is measured in the form of torque, and corresponds to the respective viscosity.
  • the sample is generally preheated for one minute to 100° C.; the measurement takes a further 4 minutes, the temperature being kept constant here.
  • the viscosity is stated together with the respective test conditions, an example being ML (1+4) 100° C. (Mooney viscosity, large rotor, preheat time and test time in minutes, test temperature).
  • the same test can moreover be used as described above to measure the scorch performance of a mixture.
  • the selected temperature was 130° C.
  • the rotor runs until, after the torque value has passed through a minimum, it has increased to 5 Mooney units above the minimum value (t5).
  • a scorch time that is advantageous for practical purposes is mostly more than 300 seconds, and when minimization of processing risk and the cost of time are taken into account this should be less than 1000 seconds.
  • the MDR (moving die rheometer) vulcanization profile and analytical data associated therewith are measured in a MDR 2000 Monsanto rheometer in accordance with ASTM D5289-95.
  • the full vulcanization time determined is the time at which 95% of the rubber has been crosslinked.
  • the selected temperature was 170° C.
  • the hardness of the rubber mixture of the invention was determined by producing milled sheets of thickness 6 mm from the rubber mixture in accordance with formulations of table 1. Test samples of diameter 35 mm were out from the milled sheets, and the Shore A hardness of these was determined by using a digital Shore hardness tester (Zwick GmbH & Co. KG, Ulm). The hardness of a rubber vulcanizate provides a first indication of its stiffness.
  • the tensile test serves directly to determine the loading limits of an elastomer, and is carried out in accordance with DIN 53504.
  • the increase in length at break is divided by the initial length to give elongation at break.
  • the force required for particular stages of elongation mostly 50, 100, 200, and 300%, is also determined, and expressed as modulus (tensile strength at the stated elongation of 300%, or 300 modulus).
  • Dynamic test methods are used to characterize the deformation behavior of elastomers under periodically changing loads. An externally applied stress changes the conformation of the polymer chain.
  • the loss factor tan ⁇ is determined indirectly here by way of the ratio of loss modulus G′′ to storage modulus G′.
  • the loss factor tan ⁇ at 60° C. is associated with rolling resistance and should be as low as possible.
  • Abrasion gives an indication of wear, and thus of product lifetime. Abrasion was determined in accordance with DIN 53516. A low value is desirable for economic and environmental reasons.
  • Apparatus 500 ml four-necked flask with thermometer, dropping funnel with pressure equalizer, reflux condenser with gas outlet attachment (bubble counter), and hose, stirrer, gas inlet tube
  • the product was analyzed by RP-HPLC and time-of-flight mass spectrometry (TOF MS).
  • the percentage data for the compounds of the formula (I) are derived from the HPLC area percentages, using RI detector.
  • Apparatus 500 ml four-necked flask with thermometer, dropping funnel with pressure equalizer, reflux condenser with gas outlet attachment (bubble counter), and hose, stirrer, gas inlet tube
  • the quantities used of the starting materials are based on the minimum content guaranteed by the manufacturer, e.g. ⁇ 98%. Because actual purities of the starting materials were higher, and because of inaccuracies due to rounding, the calculated yield was slightly above 100%.
  • the product was analyzed by RP-HPLC and time-of-flight mass spectrometry (TOF MS).
  • the percentage data for the compounds of the formula (I) are derived from the HPLC area percentages, using RI detector.
  • Apparatus 500 ml four-necked flask with thermometer, dropping funnel with pressure equalizer, reflux condenser with gas outlet attachment (bubble counter), and hose, stirrer, gas inlet tube
  • the polysulfide mixture (produced by analogy with Example 2) and methyl 3-mercaptopropionate were used as initial charge in the nitrogen-purged apparatus. Once the methyl 3-mercaptopropionate had dissolved completely, the disulfur dichloride was added dropwise within about 30 min at a temperature of from 20-25° C. while nitrogen was passed through the system. Adjustment of metering rate was such that a temperature of 25° C. was not exceeded. Once the reaction had ended, stirring of the mixture was continued overnight at room temperature while nitrogen was passed through the system. Treatment of the reaction solution then continued on a rotary evaporator at about 30° C. for 2 h.
  • the product was analyzed by RP-HPLC.
  • the percentage data for the compounds of the formula (I) are derived from the HPLC area percentages, using RI detector.
  • HPLC system with vacuum degasser, pump, column oven, injection system, and RI detector.
  • the mixture was passed to a downstream roll mill, shaped to give a sheet, and stored for 24 hours at room temperature.
  • the processing temperatures here were below 60° C.
  • the third mixing stage involved further mastication at 150° C. in a kneader.

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EP12189995.9A EP2724870A1 (de) 2012-10-25 2012-10-25 Polysulfidmischungen, Verfahren zu ihrer Herstellung und Verwendung der Polysulfidmischungen in Kautschukmischungen
PCT/EP2013/071688 WO2014063983A1 (de) 2012-10-25 2013-10-17 Polysulfidmischungen, verfahren zu ihrer herstellung und verwendung der polysulfidmischungen in kautschukmischungen

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US12319795B2 (en) 2019-12-30 2025-06-03 Bridgestone Corporation Rubber compositions prepared with a polar polysulfide crosslinking agent
US12516144B2 (en) 2020-04-30 2026-01-06 Bridgestone Corporation Rubber composition and rubber product

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EP2865540A1 (de) * 2013-10-24 2015-04-29 LANXESS Deutschland GmbH Kautschukzusammensetzung
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DE102017221233A1 (de) * 2017-11-28 2019-05-29 Continental Reifen Deutschland Gmbh Schwefelvernetzbare Kautschukmischung, Vulkanisat der Kautschukmischung und Fahrzeugreifen
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CN113214547B (zh) * 2021-06-24 2023-06-30 四川川东电缆有限责任公司 一种电缆用橡胶及制备方法

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US12516144B2 (en) 2020-04-30 2026-01-06 Bridgestone Corporation Rubber composition and rubber product

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